Hydroxy quinoline trisazo-dyestuffs



-.1.which contains United States Patent OfiFice 2 ,7 l 7,89 l PatentedSept. 13, 1955 2,717,891 HYDROXY QUINOLINE TRISAZO-DYESTUFFS WalterHanhart, Riehen, and Henri Riat, Arlesheim,-Switzerland, assignors toCiba Limited, Basel, Switzerland, a Swiss firm No Drawing. ApplicationJune 13,;1952,

Serial No. 293,425

Claims priority, application Switzerland July 5, 1951 6 Claims. (Cl.260-155) a group capable of participating in the formation of metalcomplexes, and

R3 represents the radical of a 5-hydroxynapl1thalene-7-- sulfonic acidbound in the 6-position to the azo-linkage and which is bound to thediazotizable NH2 group in at least one of the positions 1. and 2'directly or advantageously through a bridge member,

with an azo component which is capable by' itself of forming complexmetal compounds.

In the above formula the radical 'Rz is an= aromatic radical of thebenzene or naphthalene series, advantageously one which contains at most10 aryl carbon atoms. The two azo-linkages bound to Rz are inparaposition relatively to one another, and valuable trisazo dyestuffsare obtained more especially from diazodisazo-compounds of the abovecharacter whichcontain in a position vicinal to the azo linkageconnecting Ra and R a group which is capable of participating. in theformation of metal complexes, for example, a carboxylic acid group, ahydroxyl group or an alkoxy group of low molecular weight. Theamino-disazo-dyestufis of the above general formula (1) can be made bycoupling a diazo compound of an amino-monoaZo-dyestutf of the formula(2) i in which R1 and R2 have the meanings given above, with a5-hydr0xynaphthalene-7-sulfonic acid of the above character (H-Rz-NHz).

Amino-monoazo-dyestuffs of the Formula (2) can be made, for example, bycoupling a diazo compound amino group a substituent convertible into anamino group, for example, a nitro or acylamino group, with ahydroxybenzene ortho-carboxylic acid capable of coupling, and thenconverting the aforesaidsubstituent into an amino group. In this manner,for example, 4- amino-4-hydroxy-1 l-azobenzene-3 3-dicarboxylic acid canbe made from diazotized 2-nitro-5-aminobenzene-lcarboxylic acid and1-hydroxybenzene-Z-carboxylicacid, and 4-amin0-3 :4'-dihydroxy 1:1azobenzene 3' carboxylic acid can be made from diazotized 6-amino-2-methylbenzoxazole and 1-hydroxybenzene-2-carboxylic acid.

in para-position to the diazotizable Cat . bridge member.

Many amino-monoazo-dyestuffs of the Formula (2 can be made by couplingdiazotized aminohydroxybenzene-orthocarboxylic acid (R1-NH2) with amiddle component of the constitution H-R2NH2 (R1 and R2 having themeanings given above).

As amino-hydroxybenzene ortho-carboxylic acids there come intoconsideration 4-amino-l-hydroxybenzene-Z- carboxylic acids, for example,6-chloroor 6-methyl-4- amino-1-hydroxybenzene-2-carboxylic acid,4-amino-1- hydroxybenzene-2-carboxylic acid-6-sulfonic acid, butadvantageously 4-amino-l-hydroxybenzene-2-carboxylic acid itself.

The amines of the formula H-Rz-NHz serving as middle components formaking the amino-monoazodyestuffs of the Formula (2) may belong, forexample, to the naphthalene series or advantageouslythe benzene series.The substituent which is capable of participating in the formation ofmetal complexes may be a hydroxyl group or more especially an alkoxygroup. Among the alkoxy groups there are especially suitable ethoxy andabove all methoxy groups. As middle components there come intoconsideration therefore, for example, the following compounds:

Aminobenzene, l-amino-2 S-dimethylhenzene, l-amino-3-methylbenzene,

l-aminonaphthalene, 1-amino-2-methoxynaphthalene,1-amino-2-methoxynaphthalene-6- or -7-sulfonic acid, 1-amino-2-methoxyor-2-ethoxybenzene, l-amino-Z-me'thoxyor -2-ethoxy-5-methylbenzene,l-amino-Z S-dimethoxyor -2 S-diethoxybenzene,1-amino-2-ethoxy-S-methoxybenzene, 1-amino-2-methoxy-5-ethoxybenzene,l-amino-2-propyloxy-5-methoxybenzene, 1-amino-2-hydroxy-5-methylbenzene.

In the manufacture of the amino-monoazo-dyestuifs of the formula (2) bythe method last described it is generally of advantage to condutthecoupling in aweakly acid, for example, an acetic acid, medium. Whenthe middle component HR2-NH2 possesses only a small capacity forcoupling it is generally of advantage to couple it in the form of itsw-methane sulfonic acid and subsequently to split off the w-methanesulfonic acid group.

The aZo-components of the formula HR3NH2 are naphthalene derivativeswhich contain in the 5-position a hydroxy group, in the 7position asulfonic acidgroup and the diazotizable NH2 group bound either directlyto the naphthalene nucleus in the 1- or 2-position or linked with atleast one of the positions 1 and 2 by means of a As compounds of thiskind, which contain the -NH2 group bound directly to the naphthalenenucleus there may be mentioned, for example, l-amino-S-hydroxy-naphthalene-7-sulfonic acid,2-amino-5-hydroxynaphthalene-7-sulfonic acid,2-an1ino-5hydroxynaphthalene-lz7-disulfonic acid andl-chloro-2-amino-5-hydroxynaphthalene-7-sulfonic acid.

As compounds of the constitution H-R3-NH2, which contain the NH2 groupbound externally in the 2-position, that is to say, through abridgemember, there may be mentioned, for example, the following derivativesof and Z-amino5-hydr0xynaphthalene7-sulfonic acid: 1- (4' aminophenyl)amino 5 hydroXynaphtha-lene- 7:3 disulfonic acid, 2 (4 aminophenyl)amino 5- hydroxynaphthalene 7 sulfonic acid, 2 (3' aminophenyl) amino 5-hydroxynaphthalene 7 sulfonic acid, 2 (3' aminobenzoyl) amino 5hydroxynaphthalene 7 -'sulfonic acid, 2 (4' aminobenzoyl) amino- Honsandalso those compounds derived from2-amino-5-hydroxynaphthalenc-7-sulfonic acid in which the diazotizableNH2 group is bound in the 2-position and also in the l-position of thenaphthalene nucleus, that is to say bound by means of a ring condensedto the naphthalene nucleus such, for example, as in the case of thecompounds of the formulae Especially valuable is2-(4-aminophenyl)-amino-5-hydroxynaphthalene-7:3'-disulfonic acid of theformula The diazotization of the amino-monoazo-dyestuffs of theconstitution R1N N-R2NH2 can be carried out by the usual methods inthemselves known, for example, with the aid of hydrochloric acid andsodium nitrite. The diazo monoazo-compounds so obtained are then coupledin an alkaline medium, for example, a medium rendered alkaline with analkali carbonate, with an azo component of the constitution HR3-NH2.

In accordance with the process of the invention a diazodisazo-compoundof the general formula (1) is coupled with an azo component which isitself capable of forming complex metal compounds. For this purposethere comes into consideration, for example, a compound which contains asalicylic acid grouping provided that it is capable of coupling with theparticular diazo-disazo-compound used. 1-Hydroxybenzene-2-carboxylicacid itself or substitution products thereof capable of coupling, suchas 6- methyl-l-hydroxybenzene-Z-carboxylic acid, can be cou pled onlywith some of the diazo-disazo-compounds used in the invention,advantageously those which in a position vicinal to the diazotizedamino-group are free from substituents rendering the coupling difiicult,such as a sulfonic acid group.

Especially valuable as azo-components in this connection areS-hydroxyquinolines, for example, 8-hydroxyquinoline-7-sulfonic acid andabove all S-hydroxyquinoline itself.

The amino-disazo-dyestuffs are advantageously diazotized by theso-called indirect method, for example, by mixing a solution orsuspension, which contains the aminodisazo-dyestuff in the form of analkali salt and advantageously a slight excess of free alkali togetherwith the necessary quantity of nitrite, with an excess of dilutehydrochloric acid.

parts and percentages The coupling of the amino-disazo-compound with theazo-component of the above kind is advantageously carried out in analkaline medium, for example, a medium rendered alkaline with an alkalicarbonate or alkaline earth metal hydroxide, if desired with theaddition of substances assisting coupling, such as pyridine.

In general it is of advantage so to choose the starting materials thatthere is a total, of two sulfonic acid groups in the trisazo-dyestuff.

The new trisazo-dyestuffs of the invention correspond to the generalformula in which R1 represents the radical of a l-hydroxybenzene-Z-carboxylic acid,

R2 represents an aromatic radical of the benzene or naphthalene seriesin which the two azo-linkages are in para-position relatively to oneanother, and advantageously an aromatic radical which contains in aposition vicinal to the azo linkage connecting R2 and R3 a group capableof participating in the formation of metal complexes,

R3 represents the radical of a S-hydroxynaphthalene- 7-sulfonic acidbound in the 6-position to the azo linkage connecting R2 and R3, whichradical is bound in at least one of the positions 1 and 2 directly oradvantageously through a bridge member to the azo linkage connecting R3and R4, and

R4 represents the radical of an azo-component which is itself capable offorming metal complexes.

The dyestuffs are suitable for dyeing a very wide variety of materials,for example, animal fibers such as wool, silk and leather, butespecially for dyeing or printing cellulose materials such as cotton,linen, and artificial silk and staple fibers of regenerated cellulose.The dyestuffs can be treated with agents yielding metal by known methodsadvantageously on the fiber and partially in the dyebath. Withadvantage, for example, the process of U. S. Patent No. 2,148,659 may beused, in which first the dyeing and then the treatment with an agentyielding metal are carried out in the same bath. As agents yieldingmetal there come into consideration advantageously those which arestable towards alkaline solutions, such as complex copper tartrates andthe like. In some cases especially valuable dyeings can be obtained byworking according to the process in which dyeings or prints producedwith the metal-free dyestuffs are aftertreated with an aqueous solutioncontaining basic formaldehyde condensation products of compounds whichcontain at least once the atomic grouping for example, dicyandiamide ordicyandiamidine or compounds, such as cyanamide, easily convertible intocompounds containing the above atomic grouping, and also containing awater-soluble copper compound, especially a water-soluble complex coppercompound. Such a process is described, for example in British Patent No.619969.

The following examples illustrate the invention, the being by weightunless otherwise stated and the relationship between parts by weight andparts by volume being the same as that between the kilogram and liter:

Example 1 mixed with 7 parts of sodium nitrite in the form of a 4-normalsolution, and after cooling to 10-12 C. diazotization is brought aboutby pouring in dilute hydrochloric acid consisting of 35 partsof-hydrochloricacid of 30 per cent. strength; and 100 parts of water.When the diazotization has finished, coupling is carried out at -5 C.with a solution, rendered alkaline with sodium carbonate, of 41 partsof.2-(4'-aminophenyl)-amino-5- hydroxynaphthalene-7:3'-disulfonic acid.The whole is stirred for a few hours, heated tov 50C., neutralized withhydrochloric acid until approximately neutral to Brilliant Yellow paper,and the dyestuifis precipitated by the addition of 20. parts of sodiumchloride for each 100 parts by volume of coupling mixture. Aftercooling, the whole is filtered and the filter residue is washed withsodium chloride solution of. 25 per cent. strength.

The dyestulf is= dissolvedyin 1500 parts of water with the addition of12.5 parts of-sodium hydroxidesolution of 30 per cent. strength, thenmixed with 7 parts of sodium nitrite in the forrnof a 4-normal solution,diazotization is brought about at 10l5 C. by pouring in 60 parts ofhydrochloric acid of 30 per cent. strength previously diluted with 120parts: of water. The whole is stirred for a few hours, the excess ofnitrite is dCCOIl'l-w posed with sulfamici acid, at first-aweakly-hydrochloric acid solution of 1425 parts of 8.-hydroxyquinolineand then a solution :of 60 parts of sodium carbonate in 250 parts ofwater .are added. The temperature is maintained at -l0 C. by theaddition of ice. When the coupling has finished, the whole is heated toabout 70 C., parts of sodium chloride are addedwfor-every 100 parts byvolume of mixture, and-the dyestufi of the formula H000 a H is separatedbyifiltration. When dry, it is a blackish powder, which dissolvesinconcentrated sulfuricacid with a dirty blue coloration, andi in waterwith'a blueviolet coloration, and yields on cotton an after-copperedgreenish inavy blue dyeing of good .fa-stness to light and excellentfastness. to washing.

A somewhat more greenish dyeing dyestuif isobt'ained by using2:5-dimethoxy-4-amino 4'-hydroxyazobenzene 3-carboxylic acid instead of2-methyl-4-amino-5-methoxyy-4'-hydroxyazobenzene-3 -carboxylic acid.However, by using unsubstituted4-arnino-4'-hydroxyazobenzene-3'-carboxylic acid benzene instead, thereis ob- HOO OH:

HO 0 o H and .6 Example 2 38.1 parts of2-methyl-4-amino-5-rnethoxy-4'-hydroxy 1:1 azobenzene 3 carboxylicacid-5'sulfonic acid are dissolved in 700 parts of warm water withtheadditionof a quantity of a sodium hydroxide solution required forneutralization, then mixed with 7 parts of sodium nitrite-in theformof-a 4-normal solution, and after cooling to l0-I2 C. diazotizationis brought about by pouring in dilute hydrochloric acid consisting of 35parts of hydrochloric'acid of 30 per cent. strength and 100 parts ofwater. When the diazotization has; finished coupling is brought about at0-5 C. with a solution, rendered alkaline with sodium carbonate of 33parts .of 2-(4-aminophenyl)-amino-5- .hydroxynaphthalene-7-sulfonic-acid. The whole is stirred for a few hours,'heated to C., neutralizedwith hydrochloric acid until approximately neutral to Brilliant Yellowpaper, and the dyestuif is precipitated by thezaddition of 20 parts ofsodium chloride for every 100 parts by volume of mixture. After cooling,the mixture is filtered and the filter residue is washed with sodiumchloride solution. The dyestuffis dissolved in 1500 parts of water withthe addition of 12.5 parts of sodium hydroxide solution. of 30 per cent.strength, then mixed with 7 parts of sodium nitrite in the form of a4-normal solution and diazotization is brought about at lO-15 C. bypouring tin parts of hydrochloric acid of 30 per cent. strengthpreviously'diluted with 120 parts of water. The whole is stirred'"for afew/hours, the excess of :nitrite is decomposed by means of sulfamic'acid, first a weak hydrochloric .acid solution of"1'4.5 parts of 8-hydroxyquinoline and" then a solution of 60 parts of sodium carbonatein"250 parts of water-are added. The temperatureis maintained at 5-10 C.by the addition of ice. When the coupling is complete the whole isheated to about C., 10 parts of sodium chloride are added for everyparts, by volume of coupling mixture, .and the dyestuif is filtered off.When-dry it is a blackish powder which-dissolves in concentratedsulfuric acid With a dirty violet coloration and in water with a bluecoloration and dyes cotton by a single bath or 2-bath after-copperingprocess greenish navy blue tints.

--In the following table are given further valuable dyestuffs which areobtained by coupling a diazo-compound of the aminozazordyestulf in.column I with the azo componentin column-II, further diazotizing theamino-disazo-dyestufli so.obtained, and coupling the diazo compound withthe end product in columnIII. In col- 'umn' IV is given the .tint of theafter-coppered dyeing on cotton.

The 4 amino 3 :4 dihydroxy 1:1 azobenzene 3- carboxylic acid used formaking the dyestufis numbers 2 and 5 in the above table can be made asfollows:

148 parts of 6-amino-2-methylbenzoxazole of the formula \CO Ha(obtainable as described in the Journal of the Chemical Society, London,1930, page 2687) are diazotized by means of hydrochloric acid and sodiumnitrite, and then coupled in a medium rendered alkaline with sodiumcarbonate with 138 parts of l-hydroxybenzene-Z-carboxylic acid. Thedyestuif so obtained is precipitated by the addition of sodium chlorideand separated by filtration. It is then treated for 46 hours at theboiling temperature with dilute sodium hydroxide solution, wherein whichR1 represents the radical of a l-hydroxybenzene- 2-carboxylic acidattached to the adjacent N=N group in paraposition to the hydroxy group,and R2 represents an aromatic radical of the benzene series to which thetwo adjacent azo groups are bound in para-position relatively to oneanother.

2. A trisazo-dyestufi containing two sulfonic acid groups andcorresponding to the formula by the oxazole ring is split off. Then theresulting 4- amino-3 :4'-dihydroxy-l: 1'-azobenzene-3'-carboxylic acidis precipitated by the addition of hydrochloric acid and filtered 011?.The product may if desired be dried.

Example 3 In a dyebath which contains in 4000 parts of water 1.5 partsof the dyestuif as described in the first paragraph of Example 1 and 2parts of anhydrous sodium carbonate,

there are entered at C. 100 parts of cotton, the

in which R represents the radical of a l-hydroxybenzene- 2-carboxylicacid attached to the adjacent -N=N- 5 group in para-position to thehydroxy group, and R2 represents an aromatic radical of the benzeneseries to which the two azo groups are bound in para-position relativelyto one another and which contains in orthoposition to the azo groupconnecting R and the naphthalene nucleus a methoxy group.

3. The trisazo-dyestuff corresponding to the formula Hols NHQN=N 0H N=N-03H N 4. The trisazo-dyestufi corresponding to the formula H038 NH-QN=Non N=N- 0,11 N

5. The trisazo-dyestuif corresponding to the formula HOaS NHQN=N on:

temperature is raised in the course of 20 minutes to HOQN= -95" C., 40parts of crystalline sodium sulfate are added, and dyeing is carried onfor 30 minutes at 90- 70 C. Then the bath is allowed to cool to about 706. The trisazo-dyestuif corresponding to the formula References Cited inthe file of this patent UNITED STATES PATENTS 2,283,294 Straub et a1.May 19, 1942

1. A TRIS-AZO DYE STUFF CORRESPNDING TO THE FORMULA